CN105576204B - A kind of compound carbon coating cobalt phosphate lithium material of graphene and the preparation method and application thereof - Google Patents
A kind of compound carbon coating cobalt phosphate lithium material of graphene and the preparation method and application thereof Download PDFInfo
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Abstract
A kind of compound carbon coating cobalt phosphate lithium material of graphene and the preparation method and application thereof, is related to anode material for lithium-ion batteries.The compound carbon coating cobalt phosphate lithium material of graphene is made of cobalt phosphate lithium and graphene and carbon, compound by symbiosis in situ between cobalt phosphate lithium and graphene and carbon three, and graphene constitutes three-dimensional conductive network with generated in-situ carbon.Method one：It is soluble in water by lithium source, cobalt source, phosphorus source and organic carbon source, obtain solution A；It disperses graphene in absolute ethyl alcohol, obtains solution B；Solution A and B are mixed, after spray drying precursor powder, calcined under protective atmosphere, then cool to room temperature to get.Method two：Lithium source, cobalt source, phosphorus source is soluble in water, cobalt phosphate lithium presoma is obtained after spray drying；After cobalt phosphate lithium presoma is mixed with graphene and organic carbon source, calcined under protective atmosphere, then cool to room temperature to get.The compound carbon coating cobalt phosphate lithium material of graphene can be used as positive electrode and be applied to lithium ion battery.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries, more particularly, to a kind of compound carbon coating cobalt phosphate lithium material of graphene
Material and the preparation method and application thereof.
Background technology
In today that information industry is grown rapidly, battery especially secondary cell has become the weight of portable examination electronic equipment
Want component part.Energy crisis is increasingly serious, develops new, pollution-free, the reproducible energy (such as solar energy, wind energy, tide energy
Deng) be significant task of the n-th-trem relation n to human social future, and secondary cell be rationally and effectively storage and
Utilize the important medium of these new energy.In many secondary cells, lithium ion battery is due to high-energy-density, high voltage, and follows
Ring steady performance and it is most popular.
The requirement of portable electronic product and electric vehicle to long cruise duration and mileage, it is close to the energy of lithium ion battery
Degree proposes increasingly higher demands.Shown by simple computation if the specific capacity of positive electrode doubles, battery
Energy density can improve 57%, and if the specific capacity of cathode is improved to 10 times, the energy density of battery can only improve
47%.Therefore, it is the key factor for improving battery energy density to develop a kind of high-performance positive electrode.Wherein improve positive electrode
Working voltage platform be improve lithium ion battery energy density an important channel.
Polyanionic positive electrode with stable polyanion frame structure due to showing excellent safety
A kind of anode material for lithium-ion batteries system to have a great attraction can be become with good cycle performance.
1997, Padhi etc. was put forward for the first time with olivine-type LiFePO4As anode material for lithium-ion batteries.
LiFePO4 is since with high safety performance, high circulation performance, price is low, environmental-friendly feature, before having very much as one kind
The lithium ion battery of electric automobile positive electrode of scape causes the extensive research interest of people.LiFePO4Theoretical specific capacity be
170mAh/g, working voltage platform 3.4V, theory are 578Wh/kg than energy.Due to LiFePO4Working voltage platform only
There is 3.4V, the energy density of battery is relatively low, in order to further increase the energy density of battery, LiMnPO4, LiCoPO4, LiNiPO4
Also cause the interest of researcher.Wherein LiCoPO4High working voltage platform with 4.8V and higher theoretical specific capacity
(167mAh/g) can greatly improve lithium ion battery energy density (about 1.35 times of ferric phosphate lithium cell), be to have very much foreground
High-energy-density density lithium ion cell positive material.However, LiCoPO4The application of material similarly encounters polyanion material
Expect the low problem of intrinsic conductivity.The electronic conductivity of polyanionic positive electrode is relatively low, while olivine-type LiMPO4
The presence of polyanion group, which has compressed, in positive electrode is in adjacent MO together6Lithium ion transport channel between layer, reduces
The migration rate of lithium ion, the conductivity of cobalt phosphate lithium material at room temperature is about 10-9 S cm-1, it is far below metal oxide
Positive electrode LiCoO2(about 10-3 S cm-1) and LiMn2O4(about 10-5 S cm-1) conductivity at room temperature.For ferric phosphate
Lithium, this disadvantage are typically by by showing conductive layer, being solved such as carbon coating.However, research shows that cobalt phosphate lithium phase
Contact between carbon is good not as good as LiFePO4, thus carbon is difficult to effectively be coated on cobalt phosphate lithium particle surface, leads to phosphoric acid
The performance of cobalt lithium material is difficult to improve.
Currently, the synthetic method of the main current lithium manganese phosphate of cobalt phosphate lithium mainly has high temperature solid-state method, hydro-thermal method, colloidal sol-
It is prepared by the methods of gel method, coprecipitation, electrostatic spray deposition technique and microwave method.But material prepared on the whole
Chemical property is poor.To further increase cobalt phosphate material electrochemical performance, material with carbon-coated surface or compound is formed with carbon
Etc. approach be also applied to improve cobalt phosphate lithium electronic conductance.Although these approach improve the electricity of material to a certain extent
Chemical property, but usually require higher carbon content (>20%) preferable performance could be obtained.Excessively high carbon content will significantly
The tap density of cobalt phosphate lithium material is reduced, and reduces the content of active material, to significantly reduce cobalt phosphate lithium battery
Energy density, the advantages of weakening cobalt phosphate lithium material.
Invention content
The purpose of the present invention is to provide for the above-mentioned problems in the prior art, a kind of graphene composite carbon is provided
Coat cobalt phosphate lithium material and the preparation method and application thereof.
The compound carbon coating cobalt phosphate lithium material of graphene is made of cobalt phosphate lithium and graphene and carbon, cobalt phosphate lithium with
Compound by symbiosis in situ between graphene and carbon three, graphene constitutes three-dimensional conductive network with generated in-situ carbon.
One of the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene, includes the following steps：
1) soluble in water by lithium source, cobalt source, phosphorus source and organic carbon source, obtain solution A；
2) it disperses graphene in absolute ethyl alcohol, obtains solution B；
3) solution A and solution B are mixed, after spray drying, obtains precursor powder；By precursor powder under protective atmosphere
Calcining, then cools to room temperature to get the compound carbon coating cobalt phosphate lithium material of graphene.
In step 1), the lithium source can be selected from least one in lithium fluoride, lithium acetate, lithium nitrate, lithium dihydrogen phosphate etc.
Kind；The cobalt source can be selected from least one of cobalt nitrate, cobalt acetate etc.；Phosphorus source can be selected from phosphoric acid, ammonium di-hydrogen phosphate, phosphorus
At least one of acid dihydride lithium, dihydrogen phosphate, phosphoric acid hydrogen ammonia salt etc.；The organic carbon source can be selected from citric acid, sucrose, Portugal
One kind in grape sugar, ethylenediamine tetra-acetic acid etc.；The content of carbon can be cobalt phosphate lithium product by mass percentage in organic carbon source
1%~10%；Deionized water can be used in the water；It is described soluble in water preferably to be stirred at 50~100 DEG C to being completely dissolved.
In step 2), the graphene can be selected from 1~10 layer graphene or graphene microchip；The graphene presses quality
Percentage can be the 0.2%~10% of cobalt phosphate lithium product；It is described to disperse graphene in best ultrasonic vibration in absolute ethyl alcohol
Until graphene dispersion is uniform.
It is described by preferably 10~120min of stirring when solution A and solution B mixing in step 3)；The spray drying can
It is spray-dried at 120~270 DEG C；It is described precursor powder is calcined under protective atmosphere can by precursor powder nitrogen,
500~750 DEG C of 1~20h of calcining under argon gas or hydrogen-argon-mixed protective atmosphere.
The two of the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene, include the following steps：
1) lithium source, cobalt source, phosphorus source is soluble in water, after spray drying, obtain cobalt phosphate lithium presoma；
2) it after mixing gained cobalt phosphate lithium presoma with graphene and organic carbon source, is calcined under protective atmosphere, then
It is cooled to room temperature to get the compound carbon coating cobalt phosphate lithium material of graphene.
In step 1), the lithium source can be selected from least one in lithium fluoride, lithium acetate, lithium nitrate, lithium dihydrogen phosphate etc.
Kind；The cobalt source can be selected from least one of cobalt nitrate, cobalt acetate etc.；Phosphorus source can be selected from phosphoric acid, ammonium di-hydrogen phosphate, phosphorus
At least one of acid dihydride lithium, dihydrogen phosphate, phosphoric acid hydrogen ammonia salt etc.；Deionized water can be used in the water；It is described to be dissolved in water
In preferably stirred at 50~100 DEG C to being completely dissolved；The spray drying can be spray-dried at 120~270 DEG C；
In step 2), the graphene can be selected from 1~10 layer graphene or graphene microchip, and the graphene presses quality
Percentage can be the 0.2%~10% of cobalt phosphate lithium product；The organic carbon source can be selected from citric acid, sucrose, glucose, second two
One kind in amine tetraacethyl, ascorbic acid etc., the content of carbon can be cobalt phosphate lithium product by mass percentage in organic carbon source
1%~10%；The time that gained cobalt phosphate lithium presoma is mixed with graphene and organic carbon source can be 2~50h；It is described
Under protective atmosphere calcining can under nitrogen, argon gas or hydrogen argon hybrid protection atmosphere 500~750 DEG C calcining 1~20h.
The compound carbon coating cobalt phosphate lithium material of graphene can be used as positive electrode and be applied to lithium ion battery, and performance is high
Specific discharge capacity and good high rate performance.
Practical carbon amounts is the 1 of cobalt phosphate lithium quality in the compound carbon coating cobalt phosphate lithium material of graphene prepared by the present invention
~15%.
The compound carbon coating cobalt phosphate lithium material of graphene prepared by the present invention is made of cobalt phosphate lithium and graphene and carbon,
It is compound by symbiosis in situ between three.Using the good flexibility of graphene, realization is preferably combined with cobalt phosphate lithium, is passed through
Graphene constitutes three-dimensional conductive network with generated in-situ carbon, improves cobalt phosphate lithium chemical property.It provides simultaneously dry to spray
The method that dry assisted synthesizing method prepares cobalt phosphate lithium positive electrode, gained cobalt phosphate lithium positive electrode have high electric discharge specific volume
Amount height and good high rate performance, are suitable as in high specific energy anode material for lithium-ion batteries.
The present invention's has the prominent advantages that：
The closer combination of graphene and cobalt phosphate lithium is realized using the good flexibility of graphene, it is common to overcome
Carbon material is difficult to effectively be coated on cobalt phosphate lithium material, lead to material electrochemical performance difference or need a large amount of carbon coatings (>
20%) to obtain preferable performance the problem of.The compound carbon coating cobalt phosphate lithium material of synthesizing graphite alkene, production are assisted using spray drying
Object carbon content is easily controllable, and preparation process is simple, and process control is convenient, easily realizes industrialized production.It is reacted in cobalt phosphate lithium
In-situ preparation graphene and carbon coating composite material in the process, graphene constitute three-dimensional conductive network with generated in-situ carbon, only
Conductive carbon need to be added on a small quantity (practical carbon amounts is less than the 6% of cobalt phosphate lithium quality in the compound carbon coating cobalt phosphate lithium material of graphene)
It can be effectively improved cobalt phosphate lithium conductance, improve material electrochemical performance, the compound carbon coating cobalt phosphate lithium material of gained graphene
With high specific discharge capacity height and good high rate performance, it is suitable as in high specific energy anode material for lithium-ion batteries.Synthesis
The compound carbon coating cobalt phosphate lithium material of graphene and lithium metal of gained to electrode assembling at half-cell, in 3.0~5.1V voltages
Section is tested, and with 0.1C rate charge-discharges, discharge capacity is up to 145mAh/g；With 1C multiplying power dischargings, discharge capacity reaches
135mAh/g (for the 93% of 0.1C capacity).
Description of the drawings
Fig. 1 is X-ray diffraction (XRD) figure of the compound carbon coating cobalt phosphate material of graphene obtained by embodiment 1.
Fig. 2 is that the compound carbon coating cobalt phosphate material of graphene obtained by embodiment 1 is followed with 0.1C (17mA/g) and 1C multiplying powers
The first charge-discharge curve of ring.In fig. 2, curve a indicates 0.1C；Curve b indicates 1C.
Fig. 3 is the compound carbon coating cobalt phosphate material of graphene obtained by embodiment 1 with 0.1C (17mA/g) circulation
Cycle performance.In figure 3, curve a indicates Charge；Curve b indicates Discharge.
Specific implementation mode
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
Embodiment 1
LiF, Co (NO are weighed according to stoichiometric ratio3)2·6H2O, H3PO4Each 0.04mol is dissolved in 500mL water, at 80 DEG C
Stirring 2h obtains clear solution, is spray-dried at 180 DEG C, obtains cobalt phosphate lithium precursor powder.By gained cobalt phosphate
Lithium presoma and by the graphene (0.19g) of theoretical cobalt phosphate lithium weight ratio 3% and corresponding to the sucrose of 3% remaining carbon
After (0.458g) is sufficiently mixed, ethyl alcohol is uniformly mixed for solvent 500r/min ball millings 6h, by the drying of gained mixture, tabletting
Afterwards, 6h is calcined at 550 DEG C under argon gas atmosphere protection, then cools to room temperature, obtains the compound carbon coating cobalt phosphate material of graphene
Material.
Fig. 1 is X-ray diffraction (XRD) figure of the compound carbon coating cobalt phosphate material of obtained graphene.As shown in Figure 1, it adopts
The cobalt phosphate lithium positive electrode prepared with spray drying assisted synthesizing method is olivine-type rhombic system phase structure, has height
Phase purity.
By active material cobalt phosphate lithium powder, conductive agent acetylene black and binder Kynoar in mass ratio 8: 1: 1 with
Two pyrrolidones of N- methyl is that positive plate is made after being applied on aluminium foil dry, tabletting after dispersant is uniform.In argon gas atmosphere
In dry glove box, using metal lithium sheet as cathode, Celgard2300 is diaphragm, 1M LiPF6+ ethylene carbonate EC/ carbonic acid two
Methyl esters DMC (1: 1) is electrolyte, is assembled into button cell test performance.At 30 DEG C, 3.0~5.1V voltage range batteries exist
Carry out constant current charge-discharge test.Fig. 2 is the first charge-discharge curve recycled with 0.1C multiplying powers (17mA/g), as shown in Figure 2, gained
LiFePO 4 material discharge voltage is 4.8V or so, and reversible specific capacity is up to 145mAh/g, is the 87% of theoretical specific capacity.With 1C
Multiplying power discharging, discharge capacity reach 135mAh/g (for the 93% of 0.1C capacity).Meanwhile material also has preferable cycle performance
(see Fig. 3).
Embodiment 2
LiF, Co (NO are weighed according to stoichiometric ratio3)2·6H2O, H3PO4Each 0.04mol and a certain amount of sucrose
(0.458g) is dissolved in 300mL water, and 2h is stirred at 80 DEG C and obtains clear solution (solution A)；It weighs by theoretical cobalt phosphate lithium weight
Graphene (0.19g) than 3% is scattered in 200mL absolute ethyl alcohols, ultrasonic vibration certain time, until graphene dispersion is uniform
(solution B)；After 60min is mixed in solution A and solution B, it is spray-dried at 180 DEG C, gained precursor powder exists
The lower 550 DEG C of calcinings 6h of argon gas atmosphere protection, then cools to room temperature, obtains the compound carbon coating cobalt phosphate material of graphene.XRD is tied
Fruit shows that prepared cobalt phosphate lithium positive electrode is olivine-type rhombic system phase structure, has high phase purity.
Embodiment 3
LiNO is weighed according to stoichiometric ratio3, Co (NO3)2·6H2O, H3PO4Each 0.04mol is dissolved in 500mL water, 80 DEG C
Lower stirring 2h obtains clear solution, is spray-dried at 180 DEG C, obtains cobalt phosphate lithium precursor powder.By gained phosphoric acid
Cobalt lithium presoma and by the graphene (0.19g) of theoretical cobalt phosphate lithium weight ratio 3% and corresponding to the sucrose of 3% remaining carbon
After (0.458g) is sufficiently mixed, ethyl alcohol is uniformly mixed for solvent 500r/min ball millings 6h, by the drying of gained mixture, tabletting
Afterwards, 6h is calcined at 500 DEG C under argon gas atmosphere protection, then cools to room temperature, obtains the compound carbon coating cobalt phosphate material of graphene
Material.XRD has high mutually pure the results show that prepared cobalt phosphate lithium positive electrode is olivine-type rhombic system phase structure
Degree.
Embodiment 4
LiCH is weighed according to stoichiometric ratio3COO·2H2O, Co (CH3COO)2·4H2O, NH4H2PO4Each 0.04mol and one
Quantitative sucrose (0.458g) is dissolved in 300mL water, and 2h is stirred at 80 DEG C and obtains clear solution (solution A)；It weighs by theoretical phosphorus
The graphene (0.19g) of sour cobalt lithium weight ratio 3% is scattered in 200mL absolute ethyl alcohols, ultrasonic vibration certain time, until graphite
Alkene is uniformly dispersed (solution B)；After 10~60min is mixed in solution A and solution B, it is spray-dried at 180 DEG C, institute
Precursor powder 550 DEG C of calcining 6h under argon gas atmosphere protection are obtained, then cools to room temperature, obtains the compound carbon coating phosphorus of graphene
Sour cobalt material.XRD has height the results show that prepared cobalt phosphate lithium positive electrode is olivine-type rhombic system phase structure
Phase purity.
The cobalt phosphate lithium of the present invention is connected with graphene/carbon composite material in a manner of symbiosis in situ, by graphene and carbon one
It rises and constitutes three-dimensional conductive network, significantly improve the chemical property of cobalt phosphate lithium material；It provides and is closed with being spray-dried auxiliary simultaneously
At the method that method prepares cobalt phosphate lithium positive electrode, gained cobalt phosphate lithium positive electrode has high specific discharge capacity height and good
Good high rate performance, is suitable as in high specific energy anode material for lithium-ion batteries.
Claims (4)
1. the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene, it is characterised in that the compound carbon coating phosphorus of graphene
Sour cobalt lithium material is made of cobalt phosphate lithium and graphene and carbon, passes through symbiosis in situ between cobalt phosphate lithium and graphene and carbon three
Compound, graphene constitutes three-dimensional conductive network with generated in-situ carbon；The preparation method comprises the following steps：
1) soluble in water by lithium source, cobalt source, phosphorus source and organic carbon source, obtain solution A；
The lithium source is selected from least one of lithium fluoride, lithium acetate, lithium nitrate, lithium dihydrogen phosphate；The cobalt source is selected from nitric acid
At least one of cobalt, cobalt acetate；Phosphorus source is selected from phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate, dihydrogen phosphate, phosphoric acid
At least one of hydrogen ammonia salt；The one kind of the organic carbon source in citric acid, sucrose, glucose, ethylenediamine tetra-acetic acid；Have
The content of carbon is the 1%~10% of cobalt phosphate lithium product by mass percentage in machine carbon source；The water uses deionized water；It is described
Soluble in water is to be stirred at 50~100 DEG C to being completely dissolved；
2) it disperses graphene in absolute ethyl alcohol, obtains solution B；
The graphene is selected from 1~10 layer graphene or graphene microchip；The graphene is cobalt phosphate lithium by mass percentage
The 0.2%~10% of product；Described disperse graphene in absolute ethyl alcohol is ultrasonic vibration until graphene dispersion is uniform；
3) solution A and solution B are mixed, after spray drying, obtains precursor powder；Precursor powder is forged under protective atmosphere
It burns, then cools to room temperature to get the compound carbon coating cobalt phosphate lithium material of graphene.
2. the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene as described in claim 1, it is characterised in that in step
3) described by 10~120min of stirring when solution A and solution B mixing in；The spray drying is sprayed dry at 120~270 DEG C
It is dry；Described calcine under protective atmosphere precursor powder is by precursor powder in nitrogen, argon gas or hydrogen-argon-mixed protection
500~750 DEG C of 1~20h of calcining under atmosphere.
3. the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene, it is characterised in that the compound carbon coating phosphorus of graphene
Sour cobalt lithium material is made of cobalt phosphate lithium and graphene and carbon, passes through symbiosis in situ between cobalt phosphate lithium and graphene and carbon three
Compound, graphene constitutes three-dimensional conductive network with generated in-situ carbon；The preparation method comprises the following steps：
1) lithium source, cobalt source, phosphorus source is soluble in water, after spray drying, obtain cobalt phosphate lithium presoma；
The lithium source is selected from least one of lithium fluoride, lithium acetate, lithium nitrate, lithium dihydrogen phosphate；The cobalt source is selected from nitric acid
At least one of cobalt, cobalt acetate；Phosphorus source is selected from phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate, dihydrogen phosphate, phosphoric acid
At least one of hydrogen ammonia salt；The water uses deionized water；It is described it is soluble in water be at 50~100 DEG C stirring to completely it is molten
Solution；The spray drying is spray-dried at 120~270 DEG C；
2) it after mixing gained cobalt phosphate lithium presoma with graphene and organic carbon source, calcines under protective atmosphere, then cools down
To room temperature to get the compound carbon coating cobalt phosphate lithium material of graphene；
The graphene is selected from 1~10 layer graphene or graphene microchip, and the graphene is cobalt phosphate lithium by mass percentage
The 0.2%~10% of product.
4. the preparation method of the compound carbon coating cobalt phosphate lithium material of graphene as claimed in claim 3, it is characterised in that in step
2) in, the one kind of the organic carbon source in citric acid, sucrose, glucose, ethylenediamine tetra-acetic acid, ascorbic acid, organic carbon
The content of carbon is the 1%~10% of cobalt phosphate lithium product by mass percentage in source；It is described by gained cobalt phosphate lithium presoma with
The time of graphene and organic carbon source mixing is 2~50h；The calcining under protective atmosphere is mixed in nitrogen, argon gas or hydrogen argon
Close 500~750 DEG C of 1~20h of calcining under protective atmosphere.
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| CN106374106A (en) * | 2016-11-16 | 2017-02-01 | 双登集团股份有限公司 | Preparing method of lithium cobalt phosphate cathode material |
| CN107706403B (en) * | 2017-11-20 | 2020-09-25 | 中国科学院过程工程研究所 | Composite carbon material, modified electrode material prepared from same and lithium ion battery |
| CN109775682B (en) * | 2019-01-30 | 2021-01-29 | 鲍君杰 | Preparation method of lithium cobalt phosphate |
| CN112510198B (en) * | 2020-12-16 | 2022-06-17 | 武汉大学 | Positive electrode active material, aqueous solution sodium ion battery and electronic device |
| CN114620702A (en) * | 2022-03-14 | 2022-06-14 | 湖北万润新能源科技股份有限公司 | Preparation method of positive electrode material, positive plate and sodium ion battery |
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| CN103456925A (en) * | 2013-09-06 | 2013-12-18 | 新疆师范大学 | Rapid synthesis method of lithium cobaltous phosphate/carbon composite material for lithium ion battery through microwave |
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